BE1000410A3 - Mixtures brighteners optical method for their preparation, and mixed use of these products containing. - Google Patents
Mixtures brighteners optical method for their preparation, and mixed use of these products containing. Download PDFInfo
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- BE1000410A3 BE1000410A3 BE8800096A BE8800096A BE1000410A3 BE 1000410 A3 BE1000410 A3 BE 1000410A3 BE 8800096 A BE8800096 A BE 8800096A BE 8800096 A BE8800096 A BE 8800096A BE 1000410 A3 BE1000410 A3 BE 1000410A3
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- benzonitrile
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- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 230000003287 optical effect Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Substances N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims abstract description 10
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims abstract description 7
- 238000005282 brightening Methods 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 6
- NZEZRZPDYCNMAO-UHFFFAOYSA-N 4-[2-(4-formylphenyl)ethenyl]benzonitrile Chemical compound C1=CC(C=O)=CC=C1C=CC1=CC=C(C#N)C=C1 NZEZRZPDYCNMAO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002955 isolation Methods 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- -1 4-cyanostyryl Chemical group 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- KIAAMJMIIHTGBH-KQQUZDAGSA-N 4-[(e)-2-[4-[(e)-2-(4-cyanophenyl)ethenyl]phenyl]ethenyl]benzonitrile Chemical compound C1=CC(C#N)=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=C(C#N)C=C1 KIAAMJMIIHTGBH-KQQUZDAGSA-N 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 2
- OQVQNTRMZCGXIB-UHFFFAOYSA-N 2-[2-[4-[2-(4-cyanophenyl)ethenyl]phenyl]ethenyl]benzonitrile Chemical compound C1=CC(C#N)=CC=C1C=CC(C=C1)=CC=C1C=CC1=CC=CC=C1C#N OQVQNTRMZCGXIB-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJAAWBHHXIWAHM-UHFFFAOYSA-N 1,4-bis(2-phenylethenyl)benzene Chemical compound C=1C=CC=CC=1C=CC(C=C1)=CC=C1C=CC1=CC=CC=C1 IJAAWBHHXIWAHM-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YDFXKRLGZYFXOE-UHFFFAOYSA-N 2-(diethoxyphosphorylmethyl)benzonitrile Chemical compound CCOP(=O)(OCC)CC1=CC=CC=C1C#N YDFXKRLGZYFXOE-UHFFFAOYSA-N 0.000 description 1
- ZWTSHXKQOKSKMB-UHFFFAOYSA-N 2-[2-(1-cyano-2-phenylethenyl)phenyl]-3-phenylprop-2-enenitrile Chemical compound C=1C=CC=C(C(=CC=2C=CC=CC=2)C#N)C=1C(C#N)=CC1=CC=CC=C1 ZWTSHXKQOKSKMB-UHFFFAOYSA-N 0.000 description 1
- ATGJPRPJEYODEV-UHFFFAOYSA-N 2-[2-(4-formylphenyl)ethenyl]benzonitrile Chemical compound C1=CC(C=O)=CC=C1C=CC1=CC=CC=C1C#N ATGJPRPJEYODEV-UHFFFAOYSA-N 0.000 description 1
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- ZPUYDPWWJCNLFT-UHFFFAOYSA-N 3-(diethoxyphosphorylmethyl)benzonitrile Chemical compound CCOP(=O)(OCC)CC1=CC=CC(C#N)=C1 ZPUYDPWWJCNLFT-UHFFFAOYSA-N 0.000 description 1
- XSPWINZRSAKTKX-UHFFFAOYSA-N 3-[2-[4-[2-(4-cyanophenyl)ethenyl]phenyl]ethenyl]benzonitrile Chemical compound C1=CC(C#N)=CC=C1C=CC(C=C1)=CC=C1C=CC1=CC=CC(C#N)=C1 XSPWINZRSAKTKX-UHFFFAOYSA-N 0.000 description 1
- MFXWOYIWKNJHPC-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)benzonitrile Chemical compound CCOP(=O)(OCC)CC1=CC=C(C#N)C=C1 MFXWOYIWKNJHPC-UHFFFAOYSA-N 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical compound N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/65—Optical bleaching or brightening with mixtures of optical brighteners
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Detergent Compositions (AREA)
- Coloring (AREA)
Abstract
Mélanges de 51 à 98,5% en poids de 1-(4-cyanostyryl)-4-(3'-styryl)-benzène, de 48,5 à 1% en poids de 1-(4-cyanostyryl)-4-(2'-cyanostyryl)-benzène et de 0,5 à 5% en poids de 1,4-bis-(4-cyano-styryl)-benzène, un procédé pour la préparation de ces mélanges par condensation de téréphtalaldéhyde avec un 4-dialkylphosphonométhyl-benzonitrile pour donner du 4-cyano-4'-formylstilbène, lequel subit une condensation supplémentaire, directement ou après isolement, avec un 3-ou un 2-dialkylphosphonométhyl-benzonitrile, l'utilisation de ces mélanges pour l'azurage optique de fibres de polyester, et des produits contenant ces mélanges, pour l'azurage optique de fibres de polyester.Mixtures of 51 to 98.5% by weight of 1- (4-cyanostyryl) -4- (3'-styryl) -benzene, from 48.5 to 1% by weight of 1- (4-cyanostyryl) -4- (2'-cyanostyryl) -benzene and from 0.5 to 5% by weight of 1,4-bis- (4-cyano-styryl) -benzene, a process for the preparation of these mixtures by condensation of terephthalaldehyde with a 4 -dialkylphosphonomethyl-benzonitrile to give 4-cyano-4'-formylstilbene, which undergoes additional condensation, directly or after isolation, with a 3-or a 2-dialkylphosphonomethyl-benzonitrile, the use of these mixtures for optical brightening polyester fibers, and products containing these blends, for the optical brightening of polyester fibers.
Description
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MELANGES D'AZURANTS OPTIQUES, PROCEDE POUR LEUR PREPARATION, UTILISATION DE CES MELANGES ET PRODUITS LES
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CONTENANT.
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L'invention concerne des melanges d'azurants optiques, un procédé pour leur preparation, leur utilisation et des produits les contenant.
Les azurants optiques sont souvent utilises sous forme de mélangeas d'au moins deux types différents, car ces mélanges présentent un effet synergique, le degré de blanc donne par le mélange étant plus élevé que le degré de blanc obtenu par l'addition des mêmes quantites des différents constituants. On connait, diapres EP-A-30 917, des mélanges d'azurants optiques, constitues de 51 ä98, 5% en poids d'un 1, 4bis-(styryl)-benzène à substitution dissymétrique et de48, 5ä 1 % en poids d'un 1,4-bis-(styryl)-benzène à substitution symétrique. On peut citer ä titre de substituants le radical cyano et/ou un groupe carboxylate.
La présente invention a pour objet des mélanges d'azurants optiques, présentant des propriétés améliorées, et constitues de 51 a 98, 5 t en poids d'un compose de formule
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de 48, 5 ä l % en poids d'un compose de formule
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et de 0, 5 ä 5 % en poids d'un compose de formule
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Le rapport de mélange préféré est de 74 ä 84 % en poids
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du composé de formule 1 pour 25 à 15 % en poids du composé de formule 2 et 1 ä 3 % en poids du composé de formule 3.
On prépare les mélanges d'azurants optiques selon l'invention en condensant du térephtalaldehyde avec un 4-di- alkylphosphonomethyl-benzonitrile, et en poursuivant la condensation du 4-cyano-4'-formylstilbène formé, soit directement, soit après l'avoir isolé, avec un 3-dialkylphosphono-méthyl-benzonitrile et un 2-dialkylphosphonomethyl-benzonitrile. Pour isoler le produit intermediaire, on met en oeuvre la réaction du terephtalaldehyde sur le 4dialkyl-phosphonométhyl-benzonitrile en presence d'un hydroxyde de metal alcalin et d'eau, et on sépare le 4-
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cyano-4'-formyl-stilbêne précipité. 11 faut entendre par radical alkyle un radical Cl-C4, de préférence le radical méthyle ou éthyle.
On peut isoler le 4-cyano-4'-formylsti1bène, avec un bon rendement et une bonne pureté, par condensation du terephtalaldähyde avec un 4-dialkylphosphonomethyl-benzonitrile, en utilisant comme accepteur de protons des hydroxydes de metaux alcalins en solution aqueuse, comme l'hydroxyde de sodium et en particulier l'hydroxyde de potassium. Ce résultat est surprenant, car on sait que les aldéhydes aromatiques subissent des réactions de Cannizzaro avec les hydroxydes de métaux alcalins en solution aqueuse, avec formation d'acides carboxyliques et d'alcools.
La présence d'eau rend la réaction particulièrement sélective pour ce qui est de la monocondensation donnant le 4-cyano-4'-formyl-stilbène, en empêchant pratiquement la poursuite de la condensation conduisant ä du di-(cyanostyryl)-benzène symétrique, ce qui represente un avantage par rapport aux alcoolates de metaux alcalins habituellement utilises. L'utilisation supplementaire d'un alcool aliphatique inférieur ayant de 1 ä 3 atomes de carbone, en particulier de méthanol, améliore encore le procédé. Un excès de terephtalaldehyde n'est alors pas necessaire, c'est-Åa-dire qu'on utilise des quantités
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approximativement équimolaires de téréphtalaldéhyde et de phosphonate.
La température de reaction est maintenue entre 0 et 30oC, et la quantite de metal alcalin est maintenue entre l ä 2 moles par mole de téréphtalaldéhyde. La teneur en eau de l'hydroxyde de metal alcalin ä utiliser varie entre de larges limites, et de preference entre 1 et 80 %.
L'invention a aussi pour objet l'utilisation des mélanges des trois composés selon les formules l ä 3, pour l'azurage optique de fibres de polyester, ainsi que des produits pour l'azurage optique de fibres de polyester, ces melanges contenant de 51 ä 98, 5 % en poids d'un composé de formule
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48, 5 à 1 % en poids d'un compos de formule
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et 0, 5 ä 5 % en poids d'un composé de formule
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Le rapport de melange préféré est de 74 à 84 % en poids du compose de formule 1 pour 25 ä 15 % en poids du composé de formule 2 et 1 ä 3 % en poids du composé de formule 3.
Comme il est courant dans les mélanges d'azurants optiques, les différents composants peuvent être mis sous leur forme commerciale par dispersion dans un milieu liquide, par exemple l'eau. On pourra alors disperser les différents composants, puis disperser l'ensemble. Mais on peut aussi mélanger les uns aux autres les different composants de la substance finale, puis les disperser ensemble. Ce processus
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de dispersion a lieu habituellement dans des broyeurs ä billes, des moulins ä colloïde, des broyeurs ä perles ou assimilé. Les melanges selon l'invention, ou les produits qui les contiennent, conviennent d'une manière excellente à l'azurage de matières textiles ä base de polyesters linéaires.
Mais on peut aussi utiliser ces melanges ou produits sur des tissus melanges contenant des fibres de polyester linéaires.
L'application des mélanges selon l'invention s'effectue dans les conditions habituelles pour l'utilisation des azurants optiques, comme par exemple par le procédé de teinture par épuisement dans des machines de teinture, ou par application par foulardage-thermofixage. Le traitement s'effectue avantageusement en milieu aqueux, les composes etant presents sous forme finement divisee (suspensions, "microdispersions", ou éventuellement solutions). Eventuellement, on peut ajouter lors du traitement des dispersants, stabilisants, mouillants et autres adjuvants. Le traitement est habituellement mis en oeuvre ä des temperatures d'environ 20 ä 140oC, par exemple à la température d'ébullition du bain ou au voisinage de cette température.
Dans les exemples ci-après, P/V signifie poids/volume et HPLC désigne une chromatographie en phase liquide hautes performances.
Exemple
On dissout sous agitation 140 g d'une poudre d'hydroxyde de potassium (teneur en eau 12 %) dans 1600 ml de méthanol, la température stélevant de 20 C à environ 45OC.
La solution légèrement trouble obtenue est refroidie ä 200C et, en 30 minutes, on lui ajoute ä cette temperature 268 g de téréphtalaldéhyde. Puis on ajoute ä la solution jaune limpide obtenue, ä 20-25OC, en une heure et 15 minutes, une solution de 506, 5 g de 4-diéthylphosphonométhyl-benzonitrile dans 400 ml de méthanol, le produit de reaction précipitant sous forme cristalline au bout d'environ 10 ä 15 minutes. La
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suspension jaune obtenue, pâteuse, est d'abord agitee pen- dant 2 heures ä 20-25 C, puis encore pendant 2 heures ä . 40 C. Le mé1ange réactionnel est alors refroidi ä 20 C, et, ä cette temperature, dilué avec 600 ml de méthanol.
La sus- pension obtenue est essorée, et le produit d'essorage est lav6 par portions avec 1300 ml de méthanol. Le gäteau d'essorage humide ainsi obtenu est mis en suspension sous agitation dans 1440 ml de dimethylformamide, et on y ajoute
383 g de 3-diéthylphosphonométhyl-benzonitrile et 96 g de 2- diéthylphosphonométhyl-benzonitrile. Le mélange reactionnel jaune, épais, est alors chauffé ä 40OC, et, ä 40-45 C, on lui ajoute en 40 minutes sous agitation 357 g d'une solution méthanolique de méthylate de sodium (ä 30 %). Puis la sus- pension jaune obtenue est agitée pendant encore 4 heures ä 42OC, puis refroidie ä 20oC, diluée avec 1440 ml de méthanol, neutralisée avec 22 ml d'acide acétique et esso- rée.
Le produit d'essorage est bien lavé par portions avec
1800 ml de methanol (6 portions de 300 ml chacune) et séché sous vide a 100oC. On obtient 537 g d'un melange constitué de 78 % de 1-(4-cyanostyryl)-4-(3'-cyanostyryl)-benzène, de 20 % de 1-(4-cyanostyryl)-4-(2'-cyanostyryl)-benzène et de 2 % de 1,4-bis-(4-cyanostyryl)-benzène.
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MIXTURES OF OPTICAL BRIGHTENERS, PROCESS FOR THEIR PREPARATION, USE OF SUCH MIXTURES AND PRODUCTS THEREOF
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CONTAINING.
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The invention relates to mixtures of optical brighteners, a process for their preparation, their use and products containing them.
Optical brighteners are often used in the form of mixtures of at least two different types, because these mixtures have a synergistic effect, the degree of white produced by the mixture being higher than the degree of white obtained by adding the same quantities. of the different constituents. Known, diapres EP-A-30 917, mixtures of optical brighteners, consisting of 51 to 98.5% by weight of a 1,4bis- (styryl) -benzene with asymmetric substitution and 48,5 to 1% by weight a symmetrically substituted 1,4-bis- (styryl) -benzene. Mention may be made, as substituents, of the cyano radical and / or a carboxylate group.
The present invention relates to mixtures of optical brighteners, having improved properties, and consisting of 51 to 98.5 t by weight of a compound of formula
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from 48.5 to 1% by weight of a compound of formula
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and from 0.5 to 5% by weight of a compound of formula
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The preferred mixing ratio is 74-84% by weight
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of the compound of formula 1 for 25 to 15% by weight of the compound of formula 2 and 1 to 3% by weight of the compound of formula 3.
The mixtures of optical brighteners according to the invention are prepared by condensing terephthalaldehyde with a 4-di-alkylphosphonomethyl-benzonitrile, and continuing the condensation of the 4-cyano-4'-formylstilbene formed, either directly or after having isolated, with a 3-dialkylphosphono-methyl-benzonitrile and a 2-dialkylphosphonomethyl-benzonitrile. To isolate the intermediate product, the reaction of terephthalaldehyde with 4dialkyl-phosphonomethyl-benzonitrile in the presence of an alkali metal hydroxide and water is carried out, and the 4-
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precipitated cyano-4'-formyl-stilbene. An alkyl radical should be understood to mean a Cl-C4 radical, preferably the methyl or ethyl radical.
One can isolate 4-cyano-4'-formylsti1bène, with a good yield and a good purity, by condensation of terephthalaldehyde with a 4-dialkylphosphonomethyl-benzonitrile, by using as proton acceptor hydroxides of alkali metals in aqueous solution, like sodium hydroxide and in particular potassium hydroxide. This result is surprising, since it is known that aromatic aldehydes undergo Cannizzaro reactions with alkali metal hydroxides in aqueous solution, with the formation of carboxylic acids and alcohols.
The presence of water makes the reaction particularly selective with regard to the monocondensation giving 4-cyano-4'-formyl-stilbene, by practically preventing the continuation of the condensation leading to symmetrical di- (cyanostyryl) -benzene, which represents an advantage compared to the alkali metal alkoxides usually used. The further use of a lower aliphatic alcohol having 1 to 3 carbon atoms, in particular methanol, further improves the process. An excess of terephthalaldehyde is then not necessary, that is to say that quantities are used
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approximately equimolar of terephthalaldehyde and phosphonate.
The reaction temperature is maintained between 0 and 30oC, and the amount of alkali metal is maintained between 1 to 2 moles per mole of terephthalaldehyde. The water content of the alkali metal hydroxide to be used varies between wide limits, and preferably between 1 and 80%.
A subject of the invention is also the use of mixtures of the three compounds according to formulas 1 to 3, for the optical brightening of polyester fibers, as well as products for the optical brightening of polyester fibers, these mixtures containing 51 to 98.5% by weight of a compound of formula
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48.5 to 1% by weight of a compound of formula
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and 0.5 to 5% by weight of a compound of formula
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The preferred mixing ratio is 74 to 84% by weight of the compound of formula 1 for 25 to 15% by weight of the compound of formula 2 and 1 to 3% by weight of the compound of formula 3.
As is common in mixtures of optical brighteners, the various components can be put into their commercial form by dispersion in a liquid medium, for example water. We can then disperse the different components, then disperse the whole. But you can also mix the different components of the final substance with each other, then disperse them together. This process
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Dispersion usually takes place in ball mills, colloid mills, pearl mills or the like. The mixtures according to the invention, or the products containing them, are very suitable for the whitening of textile materials based on linear polyesters.
However, these blends or products can also be used on blended fabrics containing linear polyester fibers.
The application of the mixtures according to the invention is carried out under the usual conditions for the use of optical brighteners, such as for example by the process of dyeing by exhaustion in dyeing machines, or by application by padding-heat setting. The treatment is advantageously carried out in an aqueous medium, the compounds being present in finely divided form (suspensions, "microdispersions", or possibly solutions). Optionally, dispersants, stabilizers, wetting agents and other adjuvants can be added during the treatment. The treatment is usually carried out at temperatures of about 20 to 140oC, for example at or near the boiling temperature of the bath.
In the examples below, P / V means weight / volume and HPLC denotes high performance liquid chromatography.
Example
140 g of a potassium hydroxide powder (12% water content) are dissolved with stirring in 1600 ml of methanol, the temperature rising from 20 ° C. to approximately 45 ° C.
The slightly cloudy solution obtained is cooled to 200C and, in 30 minutes, 268 g of terephthalaldehyde are added to it at this temperature. Then a solution of 506.5 g of 4-diethylphosphonomethyl-benzonitrile in 400 ml of methanol is added to the clear yellow solution obtained at 20-25 ° C. in one hour and 15 minutes, the reaction product precipitating in crystalline form. after about 10 to 15 minutes. The
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The resulting yellow, pasty suspension is first stirred for 2 hours at 20-25 ° C, then again for 2 hours at. 40 C. The reaction mixture is then cooled to 20 ° C. and, at this temperature, diluted with 600 ml of methanol.
The suspension obtained is drained, and the wringing product is washed in portions with 1300 ml of methanol. The wet spinning cake thus obtained is suspended with stirring in 1440 ml of dimethylformamide, and there is added
383 g of 3-diethylphosphonomethyl-benzonitrile and 96 g of 2-diethylphosphonomethyl-benzonitrile. The thick yellow reaction mixture is then heated to 40 ° C. and, at 40 ° -45 ° C., 357 g of a methanolic solution of sodium methylate (30%) are added thereto with stirring. Then the yellow suspension obtained is stirred for a further 4 hours at 42 ° C., then cooled to 20 ° C., diluted with 1440 ml of methanol, neutralized with 22 ml of acetic acid and drained.
The spin product is washed well in portions with
1800 ml of methanol (6 portions of 300 ml each) and dried under vacuum at 100oC. 537 g of a mixture consisting of 78% of 1- (4-cyanostyryl) -4- (3'-cyanostyryl) -benzene, of 20% of 1- (4-cyanostyryl) -4- (2'- are obtained) cyanostyryl) -benzene and 2% 1,4-bis- (4-cyanostyryl) -benzene.
Claims (7)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH306/87A CH671956A5 (en) | 1987-01-29 | 1987-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE1000410A3 true BE1000410A3 (en) | 1988-11-22 |
Family
ID=4183999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE8800096A BE1000410A3 (en) | 1987-01-29 | 1988-01-28 | Mixtures brighteners optical method for their preparation, and mixed use of these products containing. |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US4867906A (en) |
| JP (1) | JP2572097B2 (en) |
| BE (1) | BE1000410A3 (en) |
| CH (1) | CH671956A5 (en) |
| DE (1) | DE3802204A1 (en) |
| FR (1) | FR2611761B1 (en) |
| GB (1) | GB2200660B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH671956A5 (en) * | 1987-01-29 | 1989-10-13 | Ciba Geigy Ag | |
| JP2501803Y2 (en) * | 1990-02-02 | 1996-06-19 | ソニー株式会社 | Cassette storage case |
| DE4330968A1 (en) * | 1993-09-13 | 1995-03-16 | Basf Ag | Brightener mixtures based on bisstyryl compounds |
| DE19609956A1 (en) * | 1995-03-24 | 1996-09-26 | Basf Ag | Optical brightener mixt. for (semi) synthetic or natural polymers |
| TWI255304B (en) * | 1999-09-06 | 2006-05-21 | Ciba Sc Holding Ag | Mixtures of fluorescent whitening agents |
| TWI250237B (en) | 1999-10-25 | 2006-03-01 | Ciba Sc Holding Ag | Mixtures of fluorescent whitening agents |
| DE10149120C1 (en) | 2001-10-05 | 2003-04-10 | Daimler Chrysler Ag | Transition area of engine or bonnet and headlights |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1415977A (en) * | 1963-10-31 | 1965-10-29 | Basf Ag | Process for the optical brightening of polyester and synthetic polyamide materials |
| EP0023027A1 (en) * | 1979-07-21 | 1981-01-28 | Hoechst Aktiengesellschaft | Mixtures of optical brighteners, their preparation and their use |
| EP0032254A1 (en) * | 1980-01-12 | 1981-07-22 | BASF Aktiengesellschaft | Method for the preparation of bis-styrylbenzenes |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE593216A (en) * | 1959-07-21 | |||
| DE1444003A1 (en) * | 1963-10-31 | 1970-03-12 | ||
| DE2929687A1 (en) * | 1979-07-21 | 1981-02-12 | Hoechst Ag | MIXTURES OF OPTICAL BRIGHTENERS |
| DE2929591A1 (en) * | 1979-07-21 | 1981-02-05 | Hoechst Ag | MIXTURES OF OPTICAL BRIGHTENERS |
| DE3070041D1 (en) * | 1979-12-13 | 1985-03-07 | Ciba Geigy Ag | Optical brighteners from bistyryl benzene, process for their preparation and their use |
| CH650792A5 (en) * | 1979-12-13 | 1985-08-15 | Ciba Geigy Ag | Optical brighteners from bisstyrylbenzene compounds and preparation thereof |
| EP0054511B1 (en) * | 1980-12-12 | 1987-05-13 | Ciba-Geigy Ag | 4-styryl-4'-vinylbifenyls, methods for their preparation and their use as optical whiteners |
| DE3313332A1 (en) * | 1983-04-13 | 1984-10-18 | Hoechst Ag, 6230 Frankfurt | Mixtures of optical brighteners for brightening polyvinyl chloride |
| US4778622A (en) * | 1986-03-21 | 1988-10-18 | Ciba-Geigy Corporation | Mixtures of fluorescent whitening agents |
| CH671956A5 (en) * | 1987-01-29 | 1989-10-13 | Ciba Geigy Ag |
-
1987
- 1987-01-29 CH CH306/87A patent/CH671956A5/de not_active IP Right Cessation
-
1988
- 1988-01-25 US US07/148,453 patent/US4867906A/en not_active Expired - Lifetime
- 1988-01-26 DE DE3802204A patent/DE3802204A1/en not_active Ceased
- 1988-01-27 GB GB8801738A patent/GB2200660B/en not_active Expired - Lifetime
- 1988-01-28 FR FR8800990A patent/FR2611761B1/en not_active Expired
- 1988-01-28 BE BE8800096A patent/BE1000410A3/en active
- 1988-01-29 JP JP63017471A patent/JP2572097B2/en not_active Expired - Fee Related
-
1990
- 1990-09-07 US US07/581,244 patent/US5072016A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1415977A (en) * | 1963-10-31 | 1965-10-29 | Basf Ag | Process for the optical brightening of polyester and synthetic polyamide materials |
| EP0023027A1 (en) * | 1979-07-21 | 1981-01-28 | Hoechst Aktiengesellschaft | Mixtures of optical brighteners, their preparation and their use |
| EP0032254A1 (en) * | 1980-01-12 | 1981-07-22 | BASF Aktiengesellschaft | Method for the preparation of bis-styrylbenzenes |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2611761B1 (en) | 1989-08-18 |
| US5072016A (en) | 1991-12-10 |
| JP2572097B2 (en) | 1997-01-16 |
| GB8801738D0 (en) | 1988-02-24 |
| CH671956A5 (en) | 1989-10-13 |
| FR2611761A1 (en) | 1988-09-09 |
| US4867906A (en) | 1989-09-19 |
| GB2200660B (en) | 1990-11-07 |
| GB2200660A (en) | 1988-08-10 |
| DE3802204A1 (en) | 1988-08-11 |
| JPS63193963A (en) | 1988-08-11 |
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| CN | Change of patent owner's name |